Modeling Parent and Metabolite Fate and Transport in Subsurface Drained Fields With Directly Connected Macropores1

Abstract: Few studies exist that evaluate or apply pesticide transport models based on measured parent and metabolite concentrations in fields with subsurface drainage. Furthermore, recent research suggests pesticide transport through exceedingly efficient direct connections, which occur when macropores are hydrologically connected to subsurface drains, but this connectivity has been simulated at only one field site in Allen County, Indiana. This research evaluates the Root Zone Water Quality Model (RZWQM) in simulating the transport of a parent compound and its metabolite at two subsurface drained field sites. Previous research used one of the field sites to test the original modification of the RZWQM to simulate directly connected macropores for bromide and the parent compound, but not for the metabolite. This research will evaluate RZWQM for parent/metabolite transformation and transport at this first field site, along with evaluating the model at an additional field site to evaluate whether the parameters for direct connectivity are transferable and whether model performance is consistent for the two field sites with unique soil, hydrologic, and environmental conditions. Isoxaflutole, the active ingredient in BALANCE^® herbicide, was applied to both fields. Isoxaflutole rapidly degrades into a metabolite (RPA 202248). This research used calibrated RZWQM models for each field based on observed subsurface drain flow and/or edge of field conservative tracer concentrations in subsurface flow. The calibrated models for both field sites required a portion (approximately 2% but this fraction may require calibration) of the available water and chemical in macropore flow to be routed directly into the subsurface drains to simulate peak concentrations in edge of field subsurface drain flow shortly after chemical applications. Confirming the results from the first field site, the existing modification for directly connected macropores continually failed to predict pesticide concentrations on the recession limbs of drainage hydrographs, suggesting that the current strategy only partially accounts for direct connectivity. Thirty‐year distributions of annual mass (drainage) loss of parent and metabolite in terms of percent of isoxaflutole applied suggested annual simulated percent losses of parent and metabolite (3.04 and 1.31%) no greater in drainage than losses in runoff on nondrained fields as reported in the literature.     

Occupational exposure to power frequency fields in some electrical transformation stations in Romania.

The aim of this study is to investigate the levels of electric and magnetic power frequency fields at 8 electrical transformation stations in the North-East counties of Romania and to check their compliance with standards. Spot measurements were carried out on both electric and magnetic fields under overhead conductors of 110-, 220- and 380-kV installations. The magnetic field levels were several orders of magnitude below the reference level for occupational exposure set by ICNIRP (International Commission on Non-Ionizing Radiation) or by Romanian regulations. In contrast, the electric field levels were about the same order of magnitude as the reference levels. In 2 electrical stations the reference level of 10 kV/m was exceeded at specific locations within the outdoor installations area. However, the additional reference level for short-time exposure included in Romanian regulations, 30 kV/m, was not exceeded.     

Effect of the allelochemicals from the macrophyte Egeria densa on the competitive interactions of pelagic and littoral cladocerans

Macrophytes release allelochemicals, which affect pelagic cladocerans such as Daphnia. Using population growth experiments, we analysed the effects of allelochemicals from the macrophyte Egeria densa on the interaction between Daphnia mendotae and three littoral cladocerans (Diaphanosoma birgei, Macrothrix triserialis and Simocephalus mixtus). We found that allelochemicals from E. densa increased the abundance of all the tested cladocerans in spite of the presence of a competitor. This effect was stronger (nearly three to four times higher than in controls) for D. birgei and M. triserialis in the absence of D. mendotae. Independent of the presence of allelochemicals, S. mixtus, but not D. birgei and M. triserialis, reduced the abundance of D. mendotae as compared to controls. The rate of population increase (r) per day was significantly elevated due to the presence of Egeria’s allelochemicals (from 0.07–0.16?d^?1 without allelochemicals against 0.12–0.24?d^?1 with allelochemicals). In our competition experiments, the rates of population increase of the cladocerans were lower than those in single-species cultures when cultured in the absence of allelochemicals. However, in the presence of allelochemicals this trend was not consistent. Thus, the positive effects of Egeria’s allelochemicals over the cladoceran populations may enhance the grazing pressure on phytoplankton.     

Dual mechanochemical immobilization of heavy metals and decomposition of halogenated compounds in automobile shredder residue using a nano-sized metallic calcium reagent

Simultaneous immobilization of heavy metals and decomposition of halogenated organic compounds in different fractions of automobile shredder residue (ASR) were achieved with a nano-sized metallic calcium through a 60-min ball milling treatment. Heavy metal (HM) immobilization and chlorinated/brominated compound (CBC) decomposition efficiencies both reached 90–100 %, after ball milling with nanometallic calcium/calcium oxide (Ca/CaO) dispersion, regardless of ASR particle size (1.0, 0.45–1.0, and 0.250 mm). Concentrations of leachable HMs substantially decreased to a level lower than the regulatory standard limits (Co and Cd 0.3 mg L⁻¹; Cr 1.5 mg L⁻¹; Fe, Pb, and Zn 3.0 mg L⁻¹; Mn and Ni 1 mg L⁻¹) proposed by the Korean hazardous waste elution standard regulatory threshold. Scanning electron microscopy with energy-dispersive X-ray spectroscopy (SEM-EDS) element maps/spectra showed that while the amounts of HMs and CBCs detectable in ASR significantly decreased, the calcium mass percentage increased. X-ray powder diffraction (XRD) patterns indicate that the main fraction of enclosed/bound materials on ASR includes Ca-associated crystalline complexes that remarkably inhibit HM desorption and simultaneously transform dangerous CBCs into harmless compounds. The use of a nanometallic Ca/CaO mixture in a mechanochemical process to treat hazardous ASR (dry conditions) is an innovative approach to remediate cross-contaminated residues with heavy metals and halogenated compounds.

     

Occurrence,elimination, and risk of anticoagulant rodenticides and drugs during wastewater treatment

Anticoagulants are biocides widely used as pest control agents in agriculture, urban infrastructures, and domestic applications for the control of rodents. Other anticoagulants such as warfarin and acenocoumarol are also used as drugs against thrombosis. After use, anticoagulants are discharged to sewage grids and enter wastewater treatment plants (WWTPs). Our hypothesis is that WWTP effluents can be a source of anticoagulants to receiving waters and that these can affect aquatic organisms and other nontarget species. Therefore, the objective of the present study was to determine the occurrence of 11 anticoagulants in WWTPs receiving urban and agricultural wastewaters. Warfarin was the most ubiquitous compound detected in influent waters and was partially eliminated during the activated sludge treatment, and low nanograms per liter concentration were found in the effluents. Other detected compounds were coumatetralyl, ferulenol, acenocoumarol, flocoumafen, brodifacoum, bromadiolone, and difenacoum at concentrations of 0.86–87.0 ng L^?1. Considering water volumes of each WWTP, daily emissions were estimated to be 0.02 to 21.8 g day^?1, and thus, WWTPs contribute to the loads of anticoagulants to receiving waters. However, low aquatic toxicity was observed using Daphnia magna as a model aquatic organism.     

Degradation of Polylactic Acid (PLA) Plastic in Costa Rican Soil and Iowa State University Compost Rows

In this study the degradation of polylactic acid (PLA) plastic films in Costa Rican soil and in a leaf composting environment was investigated. Three types of PLA films were used: Ch-I, (PLA monolayer plastic films from Chronopol, Golden, CO), GII (PLA trilayer plastic films from Cargill Dow Polymers LLC, Minnetonka, MN), and Ca-I (PLA monolayer plastic films from Cargill Dow Polymers LLC). The average soil temperature and moisture content in Costa Rica were 27°C and 80%, respectively. The average degradation rate of PLA plastic films in the soil of the banana field was 7675 M _w/week. Two compost rows were set up at the Iowa State University (ISU) (Ames) compost site. Temperature and relative humidity of the compost rows were kept at 55 ± 5°C and 50 ± 10% RH, respectively. The degradation rates of GII and Ca-I in the compost rows were 113,290 and 71,283 M _w/week, respectively. Therefore, it was estimated that in Costa Rican soil and in compost rows, PLA would be visibly degraded in 6 months and in 3 weeks, respectively.     

Interrelationship of macropores and subsurface drainage for conservative tracer and pesticide transport

Macropore flow results in the rapid movement of pesticides to subsurface drains, which may be caused in part by a small portion of macropores directly connected to drains. However, current models fail to account for this direct connection. This research investigated the interrelationship between macropore flow and subsurface drainage on conservative solute and pesticide transport using the Root Zone Water Quality Model (RZWQM). Potassium bromide tracer and isoxaflutole, the active ingredient in BALANCE herbicide [(5-cyclopropyl-4-isoxazolyl) [2(methylsulfonyl)-4-(trifluoromethyl)phenyl] methanone], with average half-life of 1.7 d were applied to a 30.4-ha Indiana corn (Zea mays L.) field. Water flow and chemical concentrations emanating from the drains were measured from two samplers. Model predictions of drain flow after minimal calibration reasonably matched observations (slope = 1.03, intercept = 0.01, and R(2) = 0.75). Without direct hydraulic connection of macropores to drains, RZWQM under predicted bromide and isoxaflutole concentration during the first measured peak after application (e.g., observed isoxaflutole concentration was between 1.2 and 1.4 mug L(-1), RZWQM concentration was 0.1 mug L(-1)). This research modified RZWQM to include an express fraction relating the percentage of macropores in direct hydraulic connection to drains. The modified model captured the first measured peak in bromide and isoxaflutole concentrations using an express fraction of 2% (e.g., simulated isoxaflutole concentration increased to 1.7 mug L(-1)). The RZWQM modified to include a macropore express fraction more accurately simulates chemical movement through macropores to subsurface drains. An express fraction is required to match peak concentrations in subsurface drains shortly after chemical applications.     

New international long-term ecological research on air pollution effects on the Carpathian Mountain forests,Central Europe

An international cooperative project on distribution of ozone in the Carpathian Mountains, Central Europe was conducted from 1997 to 1999. Results of that project indicated that in large parts of the Carpathian Mountains, concentrations of ozone were elevated and potentially phytotoxic to forest vegetation. That study led to the establishment of new long-term studies on ecological changes in forests and other ecosystems caused by air pollution in the Retezat Mountains, Southern Carpathians, Romania and in the Tatra Mountains, Western Carpathians on the Polish-Slovak border. Both of these important mountain ranges have the status of national parks and are Man & the Biosphere Reserves. In the Retezat Mountains, the primary research objective was to evaluate how air pollution may affect forest health and biodiversity. The main research objective in the Tatra Mountains was to evaluate responses of natural and managed Norway spruce forests to air pollution and other stresses. Ambient concentrations of ozone (O(3)), sulfur dioxide (SO(2)), nitrogen oxides (NO(x)) as well as forest health and biodiversity changes were monitored on densely distributed research sites. Initial monitoring of pollutants indicated low levels of O(3), SO(2), and NO(x) in the Retezat Mountains, while elevated levels of O(3) and high deposition of atmospheric sulfur (S) and nitrogen (N) have characterized the Tatra Mountains. In the Retezat Mountains, air pollution seems to have little effect on forest health; however, there was concern that over a long time, even low levels of pollution may affect biodiversity of this important ecosystem. In contrast, severe decline of Norway spruce has been observed in the Tatra Mountains. Although bark beetle seems to be the immediate cause of that decline, long-term elevated levels of atmospheric N and S depositions and elevated O(3) could predispose trees to insect attacks and other stresses. European and US scientists studied pollution deposition, soil and plant chemistry, O(3)-sensitive plant species, forest insects, and genetic changes in the Retezat and Tatra Mountains. Results of these investigations are presented in a GIS format to allow for a better understanding of the changes and the recommendations for effective management in these two areas.     

Emission Factors for Gasoline Light-Duty Vehicles: Experimental Program in Santiago,Chile

ABSTRACT

The emission inventory of the city of Santiago, Chile, related to mobile sources was built up using constant emission factors extracted from international literature. To improve the estimate of mobile source emissions, an experimental program was designed, consisting of transient tests on a chassis dynamometer over a sample of about 166 vehicles, applying 9 local driving cycles with average speeds of 3-80 km/hr, and experimentally determined in previous research carried out by the authors. An analysis of the influence of fuel inlet technology, and a year time-length model over emissions, was undertaken. We proposed emission factors as a function of average speed and of CO, THC, and NO_x for catalytic and noncatalytic light-duty gasoline vehicles, disaggregated on commercial and private cars. A comparative analysis with emission factors obtained for the application of the COPERT II and AP-42 models was also presented. Our current analysis gives solid evidence indicating that to obtain a reasonable accuracy on emission estimates and calculations, local emission factors must be used.